TWI418935B - Low temperature curable photosensitive resin composition and dry film manufactured by using the same - Google Patents

Description

Low temperature curing photosensitive resin composition and dry film prepared thereby

The present invention relates to a photosensitive resin composition and a dry film formed therefrom. In particular, the present invention relates to a photosensitive resin composition which can be cured at a low temperature to provide process safety and handling convenience, and which has excellent bending resistance, solder resistance, and pattern filling characteristics, and Excellent heat resistance and mechanical properties; and dry film prepared therefrom.

Because polyamines and their precursors have excellent durability, heat resistance, flame retardancy, and mechanical and electronic properties, polymethyleneamine and its precursors can be preferentially made into a base film for printed circuit boards. And it is widely combined with a cover film of a semiconductor device or a multilayer circuit board.

In recent years, in order to improve the flatness and positional accuracy of a circuit pattern, a photosensitive resin protective film (photoimageable cover film) of a circuit board is produced using a photolithography process. Photosensitive protective films for circuit boards should meet certain necessary conditions such as excellent durability, heat resistance, flame retardancy, and mechanical and electronic properties.

Usually, on a copper foil laminate (CCL), a type of film that thermally compresses a liquid or thermally compresses the photosensitive resin composition, performs ultraviolet light exposure along the pattern, develops, cleans, dries with a developer, and A heat curing reaction is performed to prepare a photosensitive protective film for a circuit board. Thereafter, precise holes required for connection to a circuit can be accurately formed at predetermined positions.

The photosensitive resin composition used in the photosensitive protective film for a circuit board can be obtained by adding an acrylate film to an epoxy resin by using a ruthenium film in a conventional art. However, since the cured resin produced by this method has low thermal resistance, the resin can be discolored in the soldering process and separated from the circuit. In addition, such a resin cannot be used for repeated folding portions due to lack of elasticity and bending resistance. Therefore, the composition containing an acrylate and an epoxy resin for use in a circuit board can be limited only to the use of a soft photosensitive protective film.

In order to solve these problems, there is a need for a polyimide resin having high thermal resistance, bending resistance, and good dielectric properties as a conventional protective film for circuit patterns. However, the most important problem in the photosensitive resin composition for a circuit board protective film is that it needs to be carried out in a high temperature process.

It is used in the production of polyimine photosensitive resin, which uses a polyamidene precursor of polylysine to increase its formability and make it easy to express photosensitivity; in addition, the polyamidization of poly-proline The curing process is usually carried out at a temperature of 300 to 350 ° C or higher, or at a temperature of 250 ° C or above.

In the process of preparing a printed circuit board (PCB), considering the oxidation and degradation of the copper circuit, the protective film is coated or laminated on the patterned copper at a temperature of 200 ° C or below, however, poly-proline Curing processes that require higher temperatures above 250 ° C or above become a limitation. Therefore, there is a need for a new method to reduce the temperature required for the curing stage.

The present invention provides a photosensitive resin composition which can be cured at a low temperature to provide process safety and handling convenience, and which has excellent elasticity, solder resistance and pattern filling characteristics, and has excellent heat resistance and Mechanical properties.

Further, the present invention provides a dry film comprising a cured resin product of one of the above-mentioned photosensitive resin compositions.

Furthermore, the present invention provides a multilayer printed circuit board, a flexible printed circuit board, a flexible printed circuit board, and a laminate for a semiconductor.

The present invention provides a photosensitive resin composition comprising: a polyaminic acid comprising a specific repeating unit; a heterocyclic amine compound; a methyl acrylate-based compound; a methyl acrylate-based compound having more than one carbon atom system a double bond; a photoinitiator; and an organic solvent.

Further, the present invention provides a dry film comprising a cured resin product of one of the above-mentioned photosensitive resin compositions.

Furthermore, the present invention provides a multilayer printed circuit board, a flexible printed circuit board, a flexible printed circuit board, and a laminate for a semiconductor.

Hereinafter, a photosensitive resin composition, and a dry film and a multilayer printed circuit board comprising the cured resin product prepared therefrom will be described in more detail in a specific embodiment.

The present invention provides a photosensitive resin composition according to an embodiment, wherein the photosensitive resin composition comprises: polyamic acid, the polyamic acid comprises a repeating unit, and the repeating unit is as in Chemical Formula 1. A heterocyclic amine compound selected from the group consisting of pyridine, triazole, imidazole, quinoline, and triazine ( Triazine), and the heterocyclic amine compound is unsubstituted or substituted by at least one functional group, and the functional group is selected from the group consisting of an alkyl group, a hydroxyl group, and a An oxime-derivative group; a (metha) acrylate-based compound having a carbon atom between one or more double bonds; Starting agent; and an organic solvent.

In Chemical Formula 1, X ₁ is a tetravalent organic group, and X ₂ is a divalent organic group containing one aromatic ring.

The present inventors have found that the curing temperature of the photosensitive resin composition of the present invention can be reduced to 200 by using a mixture of polyaminic acid, a specific heterocyclic amine compound and a methyl acrylate-based compound containing a specific repeating unit. °C or less to provide process safety, ease of operation, and excellent development, and to provide flexibility and sensitivity of the resin, which can be filled with irregular patterns due to improved fluidity of the resin.

The heterocyclic amine compound may comprise: pyridine, triazole, imidazole, quinoline, and triazine, and the heterocyclic amine compound is unsubstituted or at least A monofunctional group selected from the group consisting of a C1-C10 alkyl group, a hydroxyl group, and an oxime-derivative group . When the photosensitive resin composition uses a heterocyclic amine compound, it can accelerate the curing process and allow it to proceed at a temperature of 200 ° C or below. Preferably, the heterocyclic amine compound may be a heterocyclic aromatic amine compound which is unsubstituted or substituted by a functional group such as pyridine, triazole, imidazole, quinoline. ), and triazine.

The heterocyclic amine compound may be separated from the compound having a mercapto group, and the compound having a sulfur group should be cured at a relatively high temperature, and the polymer resin in the dry film may be sticky due to the nature of the sulfur group. Sex. The sulfur-substituted compounds used in the conventional field cannot have a large influence on the polyimidization of poly-proline, and thus the temperature required for curing cannot be lowered. Conversely, the above heterocyclic amine compound accelerates the polyamidation of polyphthalic acid, thereby simplifying the curing reaction of the photosensitive resin composition.

Meanwhile, in Chemical Formula 1, X ₁ is a tetravalent organic group, and preferably, the tetravalent organic group may be selected from the group consisting of Chemical Formulas 3 to 15.

[Chemical Formula 3]

[Chemical Formula 8]

[Chemical Formula 13]

In Chemical Formula 15, Y ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH And -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -COO(CH ₂ ) _n3 OCO-, and each of n1, n2 and n3 is independently an integer of from 1 to 5.

In Chemical Formula 1, X ₂ is a divalent organic group containing one aromatic ring, and preferably, the divalent organic group may be selected from the group consisting of Chemical Formulas 16 to 19.

[Chemical Formula 16]

In Chemical Formulas 17 to 19, Y ₁ , Y ₂ and Y ₃ are the same or different, and each of Y ₁ , Y ₂ and Y ₃ is independently a single bond, -O-, -CO-, -S- , -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -COO(CH ₂ ) _n3 OCO-, and each of n1, n2 and n3 is independently an integer of 1 to 5.

The polyamine contained in the chemical formula 1 may be obtained by reacting at least two bisamine compounds containing an aromatic ring with at least one acid dianhydride containing an aromatic ring. For example, the repeating unit contained in the polyglycolic acid represented by Chemical Formula 1 can be obtained by reacting at least two kinds of bisamine compounds represented by Chemical Formula 30 with at least one acid anhydride represented by Chemical Formulas 31 and 32.

[Chemical Formula 30]

H ₂ NX ₂ -NH ₂

In Chemical Formula 30, X ₂ is as shown in Chemical Formula 1.

An example of a specific bisamine compound may be at least two groups selected from the group consisting of p-phenylenediamine (p-PDA) and m-phenylenediamine (m-PDA). 4-4'-oxydianiline (4-4'-oxydianiline (4-4'-ODA)), 3-4'-oxydipaniline (3-4'-oxydianiline (3-4'-ODA) )), 2,2-bis-(4-[4-aminophenoxy]-phenyl)propane (BAPP), 1, 3-bis-(4-aminophenoxy)-benzene (1,3-bis-(4-aminophenoxy)benzene (TPE-R)), 1,4-bis-(4-aminophenoxy)benzene ( 1,4-bis-(4-aminophenoxy)benzene(TPE-Q)), 2,2-bis-(4-[3-aminophenoxy]phenyl)indole (2,2-bis-(4- [3-aminophenoxy]phenyl)sulfone (m-BAPS)), and similar compounds, but this example is not limited thereto.

[Chemical Formula 32]

In Chemical Formula 32, Y ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH And -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -COO(CH ₂ ) _n3 OCO-, and each of n1, n2 and n3 is independently an integer of from 1 to 5.

For example, the anhydride compound comprises at least one compound selected from the group consisting of pyromlitic dianhydride, 3,3'-4,4'-biphenyltetracarboxylic dianhydride. (3,3'-4,4'-biphenyltetracarboxylic dianhydride), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylbiphenyloxy)diphthalic anhydride (4,4'-(4, 4'-isopropylbiphenoxy) biphthalic anhydride)), 2,2'-bis-(3,4-dicarboxylphenyl)hexafluoropropane dianhydride (2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane di -anhydride), ethylene glycol bis-(anhydro-trimellitate (TMEG)), and similar compounds, but not limited thereto.

The preparation of polylysine can be prepared by organic synthesis methods well known in the art. For example, the preparation of polylysine may be carried out by dissolving one or more bisamine compounds of the formula 30 in a solvent, and reacting one or more dianhydrides of the formula 31 or the formula 32. Preferably, the bisamine compound and the dianhydride compound are initially reacted at a temperature ranging from 0 to 5 ° C, and are usually allowed to continue to react for 24 hours, or at a temperature ranging from 10 to 40 ° C until the reaction is completed. Herein, it is preferred to mix the bisamine compound and the dianhydride compound with a molar ratio of 1:0.9 to 1:1.1, if the molar ratio of the bisamine compound to the dianhydride compound is less than 1:0.9, due to the molecular weight thereof Very low, may make it difficult to make polyimides with excellent mechanical properties. Conversely, if the molar ratio of the bisamine compound to the dianhydride compound is higher than 1:1.1, the desired coating and handling process may become difficult due to its high viscosity.

The solvent used for preparing the polyamic acid may be at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N, N-di N,N-dimethyl acetamide (DMAc), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl Dimethyl sulfoxide (DMSO), cyclohexane, acetonitrile, and mixtures thereof, but are not limited thereto.

The number average molecular weight (Mn) of the polyamic acid is preferably in the range of from 2,000 to 300,000, more preferably from 8,000 to 20,000. If the number average molecular weight (Mn) of polyamic acid is less than 2000, the physical properties and viscosity of the resulting polyamido acid composition may become low, which may weaken the physical properties of the prepared polyimine resin. In addition, if the number average molecular weight (Mn) of polyamic acid is higher than 300,000, poly-proline is difficult to handle due to excessive viscosity in the polyamide paint.

A polyimine comprising a repeating unit as shown in Chemical Formula 2, which can be obtained from a polylysine comprising a repeating unit (as shown in Chemical Formula 1). In the case of ruthenium imidization of polylysine, the chemical imidization is carried out by adding polyacetic acid with acetic acid anhydride and pyrimidine, followed by heating to 50 to 100 ° C; The imidization system coats the polyaminic acid solution onto a substrate, which is then placed in an oven at 100 to 250 ° C or on a hot plate.

In Chemical Formula 2, X ₁ and X ₂ are as defined in Chemical 1.

As described above, in the example of the heterocyclic amine compound, the heterocyclic amine compound may be a heterocyclic aromatic amines, including: pyridine, triazole, imidazole, quinoline. (quinoline), and triazine, and the heterocyclic aromatic amine compound is unsubstituted or substituted by at least one functional group, and the functional group is selected from the group consisting of: an alkyl group a hydroxyl group, and an oxime-derivative group, and preferably comprising pyridine, triazole, imidazole, quinoline, and Triazine, and the heterocyclic aromatic amine compound is unsubstituted or substituted by at least one functional group, and the functional group is selected from the group consisting of: a C1-C10 alkyl group, A hydroxyl group and an aldoxime-derivative group. In addition, the aliphatic primary or secondary amines are not sufficiently accelerated to cure the reaction or may be reacted with the backbone of the polyamine prior to the gelation reaction. Conversely, the heterocyclic amine compound provides an excellent curing acceleration effect and allows the curing process to be carried out at a temperature of 200 ° C or lower.

The oxime or aldoxime-derived group is associated with a functional group derived from hydrazine or aldoxime, respectively, and the aldoxime-derived group may comprise a monofunctional group, as shown in Chemical Formula 33:

In Chemical Formula 33, R ₁ may be hydrogen, a C1 to C10 alkyl group, or a C7 to C15 phenol alkyl group.

When the polyamic acid is used as 100 parts by weight, it may contain 0.5 to 30 parts by weight of the heterocyclic amine compound, preferably 5 to 15 parts by weight of the heterocyclic amine compound. If the content of the heterocyclic amine compound is less than 1 part by weight, the predetermined degree of curing may not be achieved; if the content of the heterocyclic amine compound exceeds 30 parts by weight, the strength of the film after curing may be weakened.

The photosensitive resin composition may contain a methyl acrylate-based compound in which a carbon atom of the methyl acrylate-based compound contains one or more double bonds. This methyl acrylate-based compound is highly compatible with poly-proline and is prepared to form a negative pattern upon exposure to ultraviolet light.

Here, the term "metha acrylate" means a compound of (metha) acrylate and acrylate.

When polylysine is used as 100 parts by weight, 5 to 200 parts by weight of a methyl acrylate-based compound can be used. If the content of the methyl acrylate-based compound is less than 5 parts by weight, the development becomes low; if the content of the methyl acrylate-based compound is more than 200 parts by weight, the mechanical properties (such as heat resistance and elasticity).

For example, the methyl acrylate based compound is 2-hydroxyethyl (metha) acrylate, benzyl (metha) acrylate, phenoxy polyethylene methyl acrylate (phenoxypolyethylene(metha)acrylate), methoxylpolypropyleneglycol(metha)acrylate, 2-hydroxypropyl(metha)acrylate, methacryloxylate Methane acryloyloxyethyl-hydrogenphthalate, 1,6-hexandioldi(metha)acrylate, bis(methacrylic acid)-( Ethandioldi (metha) acrylate, methylenebis-(metha)acrylate, neopentyllglycoldi(metha)acrylate, 2- 2-hydroxypropandioldi(metha)acrylate, isopropyldioldi(metha)acrylate, bis(methacrylic acid) - isopropyleneglycoldi(metha)acrylate, 2-hydroxyethylmethacry Late (HEMA)), phenylglycidylester acrylate (Kayarad R-128H), 1,6-hexanediol epoxy acrylate (Kayarad R-167) )), Ebecyl 9695 (epoxy acrylate oligomer diluted with carbitol acetate) or glycidyl methacrylate (metha) acrylate, but not limited to this. This methyl acrylate-based compound may be used singly or in combination of two or more of the above compounds.

The photosensitive resin composition comprises a photoinitiator, and the photoinitiator is an acetophenone-based compound, for example, 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-hydroxy-2-methyl-1-phenyl propane-1-on), 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone (1-(4-isopropylphenyl) )-2-hydroxy-2-methylpropane-1-on), 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)one (4-(2-hydroxyethoxy)-phenyl) -(2-hydroxy-2-propyl)ketone), 1-hydroxycyclohexyl phenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-( 4-methylyl-phenyl-2-morpholino-1-propanone (2-methy1-(4-methylthio)phenyl-2-morpholino-1-propane-1-on), 2-phenyl-2 Methylamine-1-(4-morpholinylphenyl)-1-butanone (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-on), 2-methyl-1 -[4-(morpholinyl)phenyl]-2-morpholinyl- 1-Acetone (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-on), and similar compounds; a biimidazole-based compound, for example: 2, 2 - bis-(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2,2-bis-(2-chlorophenyl)-4,4',5,5'-tetraphenyl Biimidazole), 2,2-bis-(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl) 1,2'-bisimidazole (( 2,2'-bis-(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole), 2,2'-bis-( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenyl-2,2'-bis-(o-chlorophenyl)-4,4',5,5'-tetra Phenyl-1,2'-bisimidazolium (2,2'-bis-(2,3-dichloro phenyl)-4,4',5,5'-tetraphenyl 2,2'-bis-(o-chlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole), and similar compounds; triazine-based compounds, for example: 3-{4-[2,4 - bis-(trichloromethyl)-s-trioxazin-6-yl]phenylthio}propionic acid (3-{4-[2,4-bis-(trichloromethyl)-s-triazine-6-yl ]phenylthio}propionic acid), 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis-(trichloromethyl)-s-triazine- 6-yl]phenylthio} Propionic acid (1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis-(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate), ethyl- 2-{4-[2,4-bis-(trichloromethyl)-s-trioxazin-6-yl]phenylthio}acetate (ethyl-2-{4-[2,4-bis- (trichloro methyl)-s-triazine-6-yl]phenylthio}acetate), 2-epoxyethylethyl-2-{4-[2,4-bis-(trichloromethyl)-s-triazine -6-yloxyethyl-2-{4-[2,4-bis-(trichloromethyl)-s-tri-azine-6-yl]phenylthio}acetate), cyclohexane Base-2-{4-[2,4-bis-(trichloromethyl)-s-trioxazin-6-yl]phenylthio}acetate (cyclohexyl-2-{4-[2,4- Bis-(trichloromethyl)-s-triazine-6-yl]phenylthi-o}acetate), benzyl-2-{4-[2,4-bis-(trichloromethyl)-s-triazine-6 -benzyl-2-{4-[2,4-bis-(trichloromethyl)-s-triazine-6-yl]phenylthi-o}acetate), 3-{chloro-4- [2,4-bis-(trichloromethyl-s-triazazine-6-yl)phenylthio]propionic acid}(3-{chloro-4-[2,4-bis-(trichloro methyl-s) -triazine-6-yl)phenylthio-]propionic acid}), 3-{4-[2,4-bis-(trichloromethyl-s-trioxazin-6-yl)phenylthio]propanamide }(3-{4-[2,4-bis-(trichloromethyl) -s-triazine-6-yl)phenylthio]propionamide}), 2,4-bis-(trichloromethyl)-6-p-methoxystyrylstyryl-s-triazine (2,4- Bis-(trichloromethyl)-6-p-methoxy styryl-s-triazine), 2,4-bis-(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3- Butyl-s-tris-triazine (2,4-bis-(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-tri-azine), 2-trichloromethyl 2-terochloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and similar compounds; An oxime-based compound such as CGI-242 and CGI-124 manufactured by Chiba Co., Ltd. of Japan. However, the photoinitiator is not limited to the above examples.

When the polyamic acid in the photosensitive resin composition is used as 100 parts by weight, 0.3 to 10 parts by weight of a photoinitiator can be used. If the content of the photoinitiator is less than 0.3 parts by weight, the methyl acrylate compound containing one or more double bonds between carbon atoms is reduced to participate in the photocuring reaction; if the content of the photoinitiator is more than 50 parts by weight, Free radicals will not participate in the curing reaction and may reduce the physical properties of the film made of the photosensitive resin.

Further, the photosensitive resin composition contains an organic solvent, and the organic solvent may be any methyl acrylate-based compound which may have one or more double bonds with polyphthalic acid, a heterocyclic amine compound, or a carbon atom, and light. The solvent for the initiator reaction, and the solvent which can be easily dried in the coating process. When the polyamic acid in the photosensitive resin composition is used as 100 parts by weight, an organic solvent may be contained in an amount of from 300 to 700 parts by weight.

The organic solvent is preferably a monopolar aprotic solvent, and the specific organic solvent comprises, for example, at least one group selected from the group consisting of N-methyl-2-pyrrolidone (N-methyl-2- Pyrrolidone), N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide (N,N-dimethylformamide), N,N-dimethylacetamide, dimethylsulphoxide, hexanemethylphosphortriamide, N-B N-acetyl-ε-caprolactam, dimethylimidazolidoneimidazolidinone, diethyleneglycoldimethylether, triethylene glycol dimethyl ether Triethyleneglycoldimethylether), γ-butyrolactone, dioxane, dioxolane, tetrahydrofuran, chloroform, and chloromethylene ), but not limited to the above solvents.

When necessary, the composition further comprises at least one additive, the additive being selected from the group consisting of: a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, and an antifoaming agent. , a leveling agent, and a primary gel.

Another embodiment of the present invention provides a ruthenium film comprising a cured resin product of a photosensitive resin composition.

This dry film is prepared by coating the photosensitive resin composition on a support using a known method and drying it to obtain a dry film. The substrate can divide a photosensitive resin composition layer into a thin strip, and the substrate preferably has excellent light transmittance, and it is preferable that the substrate has a smooth surface.

The specific substrate may be various plastic films, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, and three. Cellulose tri-acetate, cellulose di-acetate, poly(metha)acrylic acid alkyl ester, polymethacrylate copolymer (poly(poly(meth)) Metha)acrylic acid ester copolymer), polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, a polyvinyl chloride copolymer Polyvinyl chloridene copolymer, polyamide, polyimide, vinyl chloride vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene (polyvinyl fluoride) Polytrifluoroethylene), and similar compounds. Further, a composite material composed of two or more of the above compounds may be used as the substrate, and it is preferable to use a polyethylene terephthalate film having excellent light permeability as a substrate. . The thickness of the substrate is preferably in the range of 5 to 150 μm, more preferably 10 to 50 μm.

The method of coating the photosensitive resin composition is not limited to which method, and methods such as a spray method, a roll coating method, a spin coating method, a quilting coating method, a compression coating method, and a curtain coating method can be used. Cloth method, die coating method, wire bar coating method, knife coating method. Here, the conditions for drying the photosensitive resin composition depend on the composition of the photosensitive resin composition (the ratio of the kind of the organic solvent to the content), but it is preferably dried at 60 to 100 ° C for 30 seconds to 15 minutes.

The photosensitive resin composition is coated on a substrate, and dried and cured to obtain a film thickness of the dry film, and the thickness of the film is preferably in the range of 5 to 95 μm, more preferably 10 to 50 μm. If the thickness of the film is less than 5 μm, the insulating properties may be poor; if the thickness of the film is greater than 95 μm, the resolution may be lowered.

The dry film can be formed as a cover film for a semiconductor device or a multilayer circuit board, or as a polyimide film (PICL).

Another embodiment of the present invention provides a multilayer printed circuit board, flexible printed circuit board or flexible printed circuit board comprising the dry film.

Taking a multilayer printed wiring board or a flexible circuit board as an example, after pre-laminating the dry film on the circuit forming surface using a planar compression method or a roll compression method at a temperature ranging from 25 to 50 ° C, This photosensitive coating film can be formed by a vacuum lamination method at 60 to 90 °C. In the ruthenium film, in order to form a precise hole or a precise line width, a pattern can be formed by exposure using a reticle, and the amount of exposure depends on the type of light used for exposure to ultraviolet light and the thickness of the film, but usually exposure The amount is preferably in the range of from 100 to 1200 mJ/cm ² , more preferably from 100 to 400 mJ/cm ² . Wherein, an electron beam, an ultraviolet ray, an X-ray, and the like can be used as the effective ray, but it is preferable to use the ultraviolet ray, and a high pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, and the like can also be used. Rays act as this light source.

The developing process after the exposure is immersed in a developing solution by using a dipping method, and the developing solution used is an aqueous alkali metal solution such as an aqueous solution of sodium hydroxide or an aqueous solution of sodium carbonate, and is subjected to a developing process using an alkali metal aqueous solution. Cleaned. Thereafter, the polyamine acid is converted into polyimine by development through a heat treatment process, and this pattern is obtained. Preferably, the temperature required for the heat treatment or the degree of hydrazide is carried out at a temperature ranging from 150 to 230 °C. At the same time, continuous heating is more effectively carried out by a change in the appropriate temperature in the 2nd to 4th stages, but in some cases, the curing reaction can be carried out at a predetermined temperature. A multilayer printed wiring board or a flexible circuit board can be obtained by the above process.

The invention can also provide a flexible circuit board comprising the dry film, a flexible circuit board or a laminated board for use in a semiconductor, the dry film can be used for a flexible circuit board, a flexible circuit board and a semiconductor laminate. Medium as a protective film or an interlayer insulating film.

The manufacturing method and composition of the flexible circuit board, the flexible circuit board, and the laminated board for semiconductor can be made using a technique known in the art, except that the dry film of the present invention can be formed as a protective film or an interlayer insulating film. .

The present invention provides a photosensitive resin composition which can be cured at a low temperature to provide process safety and handling convenience, and has excellent elasticity, solder resistance and filling pattern characteristics, and has excellent heat resistance. And mechanical properties; in addition, the present invention also provides a dry film made therefrom; and a multilayer printed circuit board comprising the dry film, a flexible printed circuit board, a flexible printed circuit board, and a laminate for a semiconductor .

The present invention will be described in more detail in conjunction with the following related embodiments. However, the scope of the invention should not be limited in any way.

<Preparation Example: Preparation of Polylysine (PAA1)>

Nitrogen gas was introduced into a four-necked round bottom flask equipped with a thermometer, a stirrer, a nitrogen inlet valve, and a powder distribution channel, and 780 g of N,N-dimethylacetamide (DMA, N, N-dimethylacetamide) was added. )) to 24.24g of 4,4'-diaminodiphenyl ether (4,4'-oxydianiline (4,4'-ODA)) and 106.84g of 1,3-bis-(4) in a four-neck round bottom flask - 1,3-bis-(4-aminophenoxy)benzene (TPE-R)), and stirred until dissolved. Thereafter, the solution was cooled to below 15 ° C, and 106.15 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was slowly added. And stirring to obtain a polyamic acid lacquer.

<Example: Preparation of photosensitive resin composition>

Example 1

100 parts by weight of the polyamic acid lacquer obtained in Preparation Example 1 and 10 parts by weight of 1,3,4-1H-triazole (1,3,4-1H-triazole) as a heterocyclic amine compound, 15 parts by weight A-BPE-20 (manufactured by Daiich Chem), 15 parts by weight of Kayarad R-128H (manufactured by Nippon Kayaku), and 0.3 weight, which are methyl acrylate-based compounds containing one or more double bonds between carbon atoms. A mixture of Igacure 651 and 0.2 part by weight of Igacure 369 was mixed, and the above compounds were mixed to obtain a photosensitive resin composition.

Thereafter, a photosensitive resin composition of 80 μm was coated on a polyethylene terephthalate (PET) film using a doctor blade, and dried in an oven at 80 ° C for 10 minutes to obtain a thickness of 25 μm. Decor film.

Example 2

In Example 2, except that 10 parts by weight (as the 100 parts by weight of the polyamic acid lacquer prepared in Preparation Example 1) of 3-hydroxypyridine was used as the heterocyclic amine compound, The ruthenium film was prepared by the same method as in Example 1 of the present invention.

Example 3

In Example 3, except that 10 parts by weight (as the 100 parts by weight of the polyamic acid lacquer prepared in Preparation Example 1) of 4-hydroxypyridine was used as the heterocyclic amine compound, The ruthenium film was prepared by the same method as in Example 1 of the present invention.

Example 4

In Example 4, except that 10 parts by weight (as the 100 parts by weight of the polyamic acid lacquer prepared in Preparation Example 1) was used as the heterocyclic amine, the isoformaldehyde O-benzyloxime was used as the heterocyclic amine. Other than the compound, the ruthenium film was prepared as in the method of Example 1 of the present invention.

Example 5

In Example 5, except that 10 parts by weight (as the 100 parts by weight of the polyamic acid lacquer prepared in Preparation Example 1) of imidazole was used as the heterocyclic amine compound, the same as in the present invention was used. The ruthenium film was prepared by the method of Example 1.

Example 6

In Example 6, except that 10 parts by weight (100 parts by weight of the polyamic acid lacquer prepared in Preparation Example 1) of 1-methylimidazole was used as the heterocyclic amine compound. The other methods were used to prepare a ruthenium film as in the method of Example 1 of the present invention.

Comparative example 1

In Comparative Example 1, a photosensitive resin composition and a dry film were prepared in the same manner as in Example 1 except that 10 parts by weight of 1,3,4-triazole (1,3,4-triazole) was not used.

Comparative example 2

A photosensitive resin was prepared in the same manner as in Example 1 except that 10 parts by weight of triethylamine was used instead of 10 parts by weight of 1,3,4-triazole (1,3,4-triazole). And dry film.

Comparative example 2

In addition to using 10 parts by weight of 1,8-diazobicyclo[5,4,0]undec-7-ene (1,8-diazobicyclo[5,4,0]onde-7-in (DBU)) A photosensitive resin composition and a dry film were prepared in the same manner as in Example 1 except that 10 parts by weight of 1,3,4-triazole (1,3,4-triazole) was used.

Comparative example 3

Except that 10 parts by weight of cyclohexyl amine (CHA) was used instead of 10 parts by weight of 1,3,4-triazole (1,3,4-triazole), the same as in Example 1 was used. Method A photosensitive resin composition and a dry film were prepared.

Comparative example 4

In addition to using 10 parts by weight of 1,8-diazobicyclo[5,4,0]undec-7-ene (1,8-diazobicyclo[5,4,0]onde-7-in (DBU)) A photosensitive resin composition and a dry film were prepared in the same manner as in Example 1 except that 10 parts by weight of 1,3,4-triazole (1,3,4-triazole) was used.

Comparative Example 5

In place of 10 parts by weight of 1,4-diazobicyclo[2,2,2]octane (DABCO), 10 parts by weight of 1,3, Except for 4-triazole (1,3,4-triazole), the photosensitive resin composition and dry film were prepared as in Example 1.

<Experimental Example 1: Measurement of physical and chemical properties of photosensitive dry film>

The dry films obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were placed on a pattern laminate of a product of 2 Copper Clad Laminate, laminated at 70 ° C for 30 seconds, and The curing was carried out in an oven at 180 ° C for 1 hour under a nitrogen atmosphere, after which the properties of the product were measured using the following measurement methods, and the measurement results will be as shown in Table 1.

Experimental Example 1: Membrane discoloration

The discoloration of this dry film will be assessed using the naked eye.

Experimental Example 2: Degree of cure of polyimine

The rate of polyamidization of polyimine was investigated using a diamond-attenuated total reflection FT-IR spectrometer (ATR FT-IR), and the rate of poly-proline reduction was compared to a poly-proline sample of standard curing conditions. To get a value.

Experimental Example 3: Developing properties

The resulting dry film on a copper foil of the vacuum lamination, and / cm ^2- exposed to 350 mJ, and the use of 1wt% aqueous sodium carbonate solution of 35 ℃ spray developed prepared dry film is developed based whether Check with a height of L/S = 50 μm / 50 μm.

Experimental Example 4: Viscosity strength

The cross cut fill of the cured dry film system was measured in accordance with JIS K5404. In particular, the cured dry film system was cut into a lattice shape of 100 um each, and attached using a tape (NICHIBANG). After the tape is peeled off, the viscous strength can be measured by calculating the number of crystal lattices of the photosensitive resin film which is torn along the tape.

Experimental Example 5: Solder heat resistance

At a temperature of 288 ± 5 ° C, a dry film laminated on a copper foil laminate (CCL) was floated in a soldering pot for 1 minute while the dry film surface was placed on top. Thereafter, the deformed dry film is detected by eye inspection.

Experimental Example 6: Bending resistance

On a FCCL pattern of L/S = 100 μm / 100 μm, the dry film was vacuum laminated, exposed, developed, and cured, and the FLEX method (0.38 R, load 500 g) (JIS C6471) was used to measure the bendability.

Experimental Example 7: Dielectric constant

The dielectric constant of the dry film obtained from the examples and the comparative examples was measured by the ASTM D150 method using an HP 4194A IMPEDENCE/GAIN-PHASE analyzer.

As shown in Table 1, the degree of dry film curing obtained by the examples was 100%. However, the degree of dry film curing obtained by the comparative example was 95% or less, thereby confirming that the curing reaction was not easily performed at 180 °C. Further, the dry film of the example after the heat curing did not change color, and the dry film of Comparative Example 3 became brown, and the development property of the dry film of Comparative Example 5 was not good.

Further, the dry film obtained from the examples has excellent viscosity, so it is difficult to separate it. On the other hand, the dry film obtained from the comparative example was less sticky because of its lower degree of curing.

Further, the dry film obtained in the examples was not deformed after being allowed to float at 288 ± 5 ° C for 1 minute due to its excellent solder heat resistance. However, the dry film obtained in the comparative example was low in solder heat resistance due to the phenomenon of separation.

The preferred embodiments of the present invention are described in detail above, but are not intended to limit the scope of the present invention. The present invention can be understood by those skilled in the art and can be based on the basic concepts within the scope of the present invention. Make various modifications or improvements.

Claims (15)

A photosensitive resin composition having a curing temperature of 200 ° C or lower for preparing a dry film, the photosensitive resin composition comprising: a polyamic acid, the polyamic acid comprising a repeating unit, The repeating unit is represented by Chemical Formula 1; a heterocyclic aromatic amine compound selected from the group consisting of pyridine, imidazole, quinoline, and a triazine, and the heterocyclic amine compound is unsubstituted or substituted by at least one functional group selected from the group consisting of an alkyl group and a hydroxyl group. And an oxime-derivative group; a (metha) acrylate-based compound, wherein the carbon atom of the methyl acrylate-based compound contains one or more double bonds; a photoinitiator; and an organic solvent; Here, in Chemical Formula 1, X ₁ is a tetravalent organic group, and X ₂ is a divalent organic group containing one aromatic ring. The photosensitive resin composition according to claim 1, wherein X ₁ is a tetravalent organic group selected from the group consisting of Chemical Formulas 3 to 15: Wherein, in Chemical Formula 15, Y ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -COO(CH ₂ ) _n3 OCO-, and each of n1, n2 and n3 is independently an integer from 1 to 5 . The photosensitive resin composition according to claim 1, wherein the X ₂ is a divalent organic group selected from the group consisting of the chemical formulas 16 to 19: Wherein, in Chemical Formulas 17 to 19, Y ₁ , Y ₂ and Y ₃ are the same or different, and each of Y ₁ , Y ₂ and Y ₃ is independently a single bond, -O-, -CO-, - S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -COO (CH ₂ ) _n3 OCO-, and each of n1, n2 and n3 is independently an integer of 1 to 5. The photosensitive resin composition according to claim 1, wherein the polyamic acid has a number average molecular weight of from 2,000 to 300,000. The photosensitive resin composition according to claim 1, wherein the methyl acrylate-based compound has one or more double bonds between carbon atoms, and the methyl acrylate-based compound is at least one selected from the group consisting of Group consisting of 2-hydroxyethyl(metha)acrylate, benzyl (metha)acrylate, phenoxypolyethylene(metha) Acrylate), methoxy polymethacryl Methoxyl polypropylene propylene (metha) acrylate, 2-hydroxypropyl (metha) acrylate, metha acryloyloxyethyl-hydrogenphthalate, 1,6-hexandioldi(metha)acrylate, ethandioldi(metha)acrylate, methylene Methylenebis-(metha)acrylate, neopentyllglycol di(metha)acrylate, 2-hydroxybis(methacrylic acid)-(propane)acrylate (2-hydroxypropandiol di(metha)acrylate), isopropyldiol di(metha)acrylate, isopropyleneglycol di(metha) Acrylate), 2-hydroxyethyl methacrylate, phenylglycidylester acrylate, epoxy acrylate (1,6-hexanedicarboxylate) Acrylate), Ebecyl 9695, and glycidyl (metha) acrylate. The photosensitive resin composition according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of an acetophenone-based compound and a double imidazole. A biimidazole-based compound, a triazine-based compound, and an oxime-based compound. The photosensitive resin composition according to claim 1, wherein the organic solvent is at least one selected from the group consisting of N-methyl N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone , N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulphoxide, hexanemethyl Hexanemethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidoneimidazolidinone, diethylene glycol dimethyl ether Diethyleneglycoldimethylether), triethyleneglycoldimethylether, γ-butyrolactone, dioxane, dioxolane, tetrahydrofuran, chloroform (chloroform), and chloromethylene. The photosensitive resin composition according to claim 1, wherein the composition comprises: 0.5 to 30 parts by weight of the heterocyclic aromatic amine compound; and 5 to 200 parts by weight based on 100 parts by weight of the polyamic acid. And a methyl acrylate-based compound comprising, by the carbon atom of the methyl acrylate-based compound, one or more double bonds; 0.3 to 10 parts by weight of a photoinitiator; and 300 to 700 parts by weight of an organic solvent. The photosensitive resin composition according to claim 1, wherein the composition further comprises at least one additive selected from the following The group consisted of: a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, and a primary anti-gelling agent. A dry film comprising a cured resin product of a photosensitive resin composition, which is a photosensitive resin composition as described in claim 1 of the patent application. The dry film of claim 10, wherein the dry film is used for a semiconductor device or a cover film of a multilayer circuit board. A multilayer printed circuit board comprising a dry film as in claim 10 of the patent application. A flexible printed circuit board comprising a dry film as in claim 10 of the patent application. A flexible printed circuit board comprising a dry film as in claim 10 of the patent application. A laminate for a semiconductor comprising a dry film as in claim 10 of the patent application.